research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 73| Part 2| February 2017| Pages 141-146
https://doi.org/10.1107/S2056989017000111

Crystal structures of two mixed-valence copper cyanide complexes with N-methyl­ethylenedi­amine

CROSSMARK_Color_square_no_text.svg
Peter W. R. Corfielda* and Alexander Sabatinoa

aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA
*Correspondence e-mail: pcorfield@fordham.edu

Edited by S. Parkin, University of Kentucky, USA (Received 6 December 2016; accepted 4 January 2017; online 10 January 2017)

The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl­ethylenedi­amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3C:C:N)tris(μ2-cyanido-κ2C:N)bis(N-methylethane-1,2-di­amine-κ2N,N′)tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuI atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra­hedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuI atoms link these units together to form the network. The CuII atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol­ecular compound (II), [(N-methylethylenediamine-κ2N,N′)copper(II)]-μ2-cyanido-κ2C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a CuII atom coordinated by two meen groups with a trigonal–planar CuI atom coordinated by CN groups. The mol­ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol­ecules. In both compounds, the bridging cyanide between the CuII and CuI atoms has the N atom bonded to CuII and the C atom bonded to CuI, and the CuII atoms are in a square-pyramidal coordination.

CCDC references: 1525492; 1525491

Similar articles

1. Chemical context

There is continuing inter­est in the synthesis and structures of coordination polymers involving CuCN networks (Etaiw et al., 2015[Etaiw, S. H., Abdou, A. N. & Badr El-din, A. S. (2015). J. Inorg. Organomet. Polym. 25, 1394-1406.], 2016[Etaiw, S. E. H., Badr El-din, A. S. & Abdou, A. N. (2016). Transition Met. Chem. 41, 413-425.]; Cai et al., 2011[Cai, J.-B., Chen, T.-T., Xie, Z.-Y. & Deng, H. (2011). Acta Cryst. E67, m1136-m1137.]). The structure determinations described here arise from our ongoing syntheses of mixed-valence copper cyanide complexes incorporating various amines, with the aim of the directed synthesis of new polymeric structures. A variety of crystal structures form from CuI,II-cyanide-multidentate amine systems, ranging from the classic three-dimensional mixed-valence structure Cu3(CN)4en2·H2O where en is ethyl­enedi­amine (Williams et al., 1972[Williams, R. J., Larson, A. C. & Cromer, D. T. (1972). Acta Cryst. B28, 858-864.]) to mol­ecular compounds such as Cu2(CN)3eten2 (Corfield & Michalski, 2014[Corfield, P. W. R. & Michalski, J. F. (2014). Acta Cryst. E70, m76-m77.]), where eten is N-ethyl­ethylenedi­amine. Syntheses involving N-methyl­ethylenedi­amine, meen, led to the formation of blue crystals of (II)[link], Cu2(CN)3meen2·H2O, which formed as elongated plates. Their structure described here is that of a mol­ecular compound very similar to the eten derivative referred to above. Syntheses with meen have also been carried out in the presence of tetra­hedral monovalent anions such as BF4− and ClO4−, in the hope that incorporation of negative ions might induce crystallization of a polymeric structure. The major or sometimes sole product in these preparations were well-formed polyhedral black crystals of (I)[link], Cu4(CN)5meen2, which we found to indeed be made up of a three-dimensional network, but, somewhat to our surprise, without any incorporation of BF4− or ClO4− anions.

[Scheme 1]

2. Structural commentary

The asymmetric units for compounds (I)[link] and (II)[link] are shown in Fig. 1[link] and Fig. 2[link]. Compound (I)[link], Cu4(CN)5meen2, crystallizes as a three-dimensional cyanide-bridged CuI network, with CuIImeen2 units covalently anchored to the network via the bridging C1—N1 group, with N1 bonded to CuII. The network is assembled from Cu2(CN)6 units, trigonal–planar Cu(CN)3 units, and square-pyramidal Cumeen2(CN) units. Compound (II)[link] crystals contain monomeric dinuclear mol­ecules of Cu2(CN)3meen2·H2O.

[Figure 1]
Figure 1
The asymmetric unit for compound (I)[link], Cu4(CN)5meen2. Ellipsoids are drawn at the probability 50% level. The cuprophilic inter­action is shown as a dashed bond.
[Figure 2]
Figure 2
The asymmetric unit for compound (II)[link], Cu2(CN)3meen2·H2O. Ellipsoids are drawn at the probability 50% level. The refined N- and O-bound hydrogen atoms are emphasized.

The dimeric Cu2(CN)6 units in (I)[link] are comprised of tetra­hedrally coordinated atoms Cu1 and Cu2 held closely together by two μ3-CN groups coordinating to both Cu atoms via C1 and C2, with short Cu ⋯ Cu distances of 2.560 (1) Å. The Cu—C and Cu—N distances listed in Table 1[link] show that the end-on CN bridging is not symmetrical, with Cu1—C1 and Cu1—C2 distances of 0.2–0.3 Å less than the corresponding bond lengths to Cu2. This asymmetry is the norm for such dimers, as noted in Corfield et al. (2016[Corfield, P. W. R., Cleary, E. & Michalski, J. F. (2016). Acta Cryst. E72, 892-896.]). The assumed cuprophilic attraction distorts the tetra­hedral coordination around Cu1, with the C1—Cu1—C2 angle opened up to 118.01 (13)°, while the N4—Cu1—N5 angle opposite is reduced to 102.67 (12)°. The situation is reversed for Cu2, where the C1—Cu2—C2 angle is 96.13 (11)° and the opposite angle C3—Cu2—C4 is increased to 128.27 (13)°.

Table 1
Selected bond lengths (Å) for (I)[link]

Cu1—C1 1.980 (3) Cu3—N2 1.942 (3)
Cu1—C2 2.042 (3) Cu3—N3ii 1.961 (3)
Cu1—N4 2.050 (3) Cu3—C5iii 1.910 (3)
Cu1—N5 2.041 (3) Cu4—N11 2.002 (3)
Cu1—Cu2 2.5599 (7) Cu4—N14 2.072 (3)
Cu2—C1 2.379 (3) Cu4—N16 2.009 (3)
Cu2—C2 2.255 (3) Cu4—N19 2.059 (3)
Cu2—C3 1.935 (3) Cu4—N1 2.292 (3)
Cu2—C4i 1.948 (3)    
Symmetry codes: (i) [-x, -y+1, z+{\script{1\over 2}}]; (ii) x, y+1, z; (iii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Trigonal coordination at Cu3 in (I)[link] is distorted, with angles ranging from 112.56 (12)° to 129.79 (13)°; the coordination is rigidly planar, however. In (II)[link], coordination at the trigonal planar CuI atom is much more regular, with angles ranging from 117.49 (7)° to 122.15 (7)°.

Both (I)[link] and (II)[link] contain CuII atoms coordinated by two bidentate meen ligands and the N atom of a bridging cyanide group, in square-pyramidal coordination. Cu atoms are 0.122 (1) and 0.220 (1) Å from the best plane through the amine N atoms in (I)[link] and (II)[link], respectively. In (I)[link], the Cu—NH(CH3) bonds are 0.05–0.07 Å longer than the Cu—NH2 bonds (Table 1[link]), whereas the corresponding bond lengths are more similar in (II)[link](Table 2[link]), as also seen in the N-ethyl complex corresponding to (II)[link], Cu2(CN)3eten2 (Corfield & Michalski, 2014[Corfield, P. W. R. & Michalski, J. F. (2014). Acta Cryst. E70, m76-m77.]).

Table 2
Selected bond lengths (Å) for (II)[link]

Cu1—C1 1.9434 (15) Cu2—N4 2.0200 (14)
Cu1—C2 1.9380 (18) Cu2—N7 2.0453 (13)
Cu1—C3 1.9414 (18) Cu2—N14 2.0262 (15)
Cu2—N1 2.2232 (14) Cu2—N17 2.0417 (14)

Coordination of the methyl­ated N atom in meen to Cu4 produces a chiral center. N atoms in the (x,y,z) atoms of (I)[link] have the R configuration, and the chelate rings have the δ conformation, with N—C—C—N torsion angles of 54.6 (4)° and 56.0 (4)°. Glide-plane-related rings will have the Sλ combination. Methyl­ated N atoms in the Cumeen2 units in (II)[link] both have the SSδδ configuration, with N—C—C—N torsion angles of −53.0 (2)° and −53.1 (2)°. The center of inversion in (II)[link] causes an equal number of mol­ecules with the RRλλ combinations. The CH3—N—C—C torsion angles in the chelate rings depend on the R/S and δ/λ combination. For an Rδ combination, this angle will be approximately −170°, and for Rλ the angle will be about −90°. These angles are reversed in sign for the Sλ and Sδ combinations. CH3—N—C—C angles are −172.8 (3) and −167.4 (3)° in (I)[link], and 175.0 (2) and 174.5 (2)° in (II)[link]. Averages for these angles in 24 Cumeen chelate rings are reviewed in the Database Survey section.

3. Supra­molecular features

In (I)[link], each dimeric Cu2(CN)6 unit is linked by the C4–N4 cyanide group to a screw-related Cu2(CN)6 unit to form chains of these units parallel to the c axis, Fig. 3[link]. Trigonally coordinated Cu3 also links the Cu2(CN)6 units together via CN bridges into single-stranded chains along the 8.231 (1) Å b axis, Fig. 4[link], similar to the double-stranded chains along the 8.356 (1) Å a axis seen in the polymeric compound (et2oenH)[Cu2(CN)3], (Corfield et al., 2016[Corfield, P. W. R., Cleary, E. & Michalski, J. F. (2016). Acta Cryst. E72, 892-896.]), where et2oen is N,N-di­ethyl­ethano­lamine. The columns are further linked together by Cu3 to form a structure with channels, into which projects the coordinated Cumeen2 unit, Fig. 3[link]. The topology around Cu3 involves three 20-membered rings. There are four close inter­actions between amine N—H bonds and bridging CN groups, with N⋯N distances ranging from 3.257 (3) to 3.479 (3) Å, which may account for the tendency for ordered CN groups in this structure. The shortest H⋯H inter­molecular contact in (I)[link] is 2.47 Å for H15B⋯H18B(−[{1\over 2}] − x, −[{1\over 2}] + y, −[{1\over 2}] + z).

[Figure 3]
Figure 3
Packing diagram for compound (I)[link], Cu4(CN)5meen2, giving a projection down the b axis. Cuprophilic inter­actions are shown as dashed bonds. For clarity, only a section of the structure perpendicular to b is shown.
[Figure 4]
Figure 4
Projection of part of the structure of compound (I)[link], Cu4(CN)5meen2 down the c axis, showing a chain along the b direction. Cuprophilic inter­actions are shown as dashed bonds.

Centrosymmetric pairs of discrete mol­ecules of (II)[link] are held together by hydrogen bonding (Table 3[link]) to the water mol­ecules, Fig. 5[link], with each water mol­ecule forming one donor and one acceptor hydrogen bond. These pairs are linked into chains via hydrogen bonds along [011], N4—H4A⋯⋯N3(1 − x, 1 − y, 2 − z)—C2(1 − x, 1 − y, 2 − z), where these four atoms are almost co-linear. Two other potentially attractive relationships between N—H bonds and cyanide groups are also shown in Fig. 5[link].

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯N2 0.68 (3) 2.13 (3) 2.810 (3) 171 (3)
N14—H14A⋯O1i 0.83 (2) 2.14 (2) 2.965 (3) 177 (2)
N4—H4A⋯N3ii 0.86 (2) 2.26 (2) 3.094 (2) 161.1 (19)
N7—H7⋯N2iii 0.810 (19) 2.460 (19) 3.162 (2) 145.7 (16)
N4—H4B⋯N3iii 0.78 (2) 2.53 (2) 3.302 (3) 170 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x+1, y+1, z.
[Figure 5]
Figure 5
Packing diagram for compound (II)[link], Cu2(CN)3meen2·H2O, looking approximately down the a axis. A hydrogen-bonded dimer is bolded, with hydrogen bonds shown as double-dashed lines. Hydrogen bonds linking dimers along the [011] direction are similarly shown. Possible attractive inter­actions between N—H groups and CN groups that would link dimers along the [110] direction are shown as single dashed lines.

4. Database survey

Searches of the Cambridge Structure Database (CSD, Version 5.35; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) yielded 53 structures containing the Mmeen fragment, where M is any metal. For 19 of these structures M = Cu (the Cumeen set) and for 19 M = Co (the Comeen set). There were four where M was a different metal, and 11 which involved duplicates or structures with no coordinates. The Cumeen set entries contained 24 chelate Cumeen rings, while the Comeen set contains 35 chelate rings.

The Cumeen set showed the same lengthening of the Cu—NH(CH3) bonds with respect to the Cu—NH2 bond lengths as found here in (I)[link], with averages of 2.010 (4) and 2.041 (4) Å, respectively. A similar difference was found for the Comeen set, where the corresponding means were 1.962 (8) and 1.998 (8) Å. Cu—N bond lengths showed no correlation with coordination numbers around Cu, which ranged from four through six. N—Cu—N angles in the Cumeen set are in a limited range of 84.0 to 86.4°, and the four such angles in the present study all lie near the middle of this range.

The average of the absolute values of the N—C—C—N torsion angles in the chelate rings for the Cumeen set is 51.6°, with a sample s.u. of 6.5°, excluding one outlier from a flat chelate ring. Corresponding angles in the present work are all within one s.u. of the mean. The mean absolute CH3—N—C—C angles for Rδ/Sλ and Rλ/Sδ combinations, respectively, in the Cumeen set are 171 (6) and 89 (5)°, where sample s.u.'s are given. Equivalent torsion angles in both structures presented here fall within one s.u. of these means.

5. Synthesis and crystallization

The compounds were synthesized by air oxidation of CuCN/NaCN/meen systems. A typical preparation of (II)[link] had CuCN (5.7 mmol) and NaCN (8.3 mmol) stirred in 6 mL of water until all solids dissolved, when 8.6 mmol of N-methyl­ethylenedi­amine (meen) in approximately 5 mL of water were added. Blue crystals in the form of extended thick plates were recovered after two days at room temperature. Crystals of (I)[link] were obtained in a similar preparation with 11.5 mmmol CuCN, 16.5 mmol NaCN, and 16.2 mmol meen, to which were added an aqueous solution containing 9.9 mmol NaClO4. Blue crystals of (II)[link] were obtained after two weeks, but after another six weeks the filtrate yielded large black polyhedral crystals of (I)[link].

Infra-red spectra obtained with a Nicolet iS50 FT–IR machine on the polymer (I)[link] showed three bands in the CN stretching region, with peaks at 2079, 2109, and 2119 cm−1. In addition, there are strong bands at 3250 and 3312 cm−1, and a weak, sharp band at 3150 cm−1, presumably all due to N-H stretching vibrations. For (II)[link], CN stretching frequencies at 2089 and 2115 cm−1 were observed.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. In (I)[link], it was apparent that several low-order reflections were partially or completely obscured by the backstop and/or subject to overload. We recollected a fast dataset to θ = 15° with the backstop pushed back, obtained the scale factor between the two datasets using reflections with θ above 5°, and replaced 27 low-angle reflections in (I)[link] with data from the fast dataset. Three low-angle reflections were not obtained in the fast dataset, and these have been omitted in the final refinement.

Table 4
Experimental details

  (I) (II)
Crystal data
Chemical formula [Cu4(CN)5(C3H10N2)2] [Cu2(CN)3(C3H10N2)2]·H2O
Mr 532.52 371.42
Crystal system, space group Orthorhombic, Pna21 Triclinic, P[\overline{1}]
Temperature (K) 303 300
a, b, c (Å) 19.509 (2), 8.2306 (13), 11.100 (2) 7.5621 (2), 8.8689 (2), 12.8098 (3)
α, β, γ (°) 90, 90, 90 94.6851 (14), 101.8607 (12), 108.3780 (13)
V (Å3) 1782.3 (5) 787.91 (3)
Z 4 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 4.72 2.70
Crystal size (mm) 0.5 × 0.4 × 0.4 0.5 × 0.4 × 0.3
 
Data collection
Diffractometer Enraf–Nonius KappaCCD Enraf–Nonius KappaCCD
Absorption correction Part of the refinement model (ΔF) (SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) Part of the refinement model (ΔF) (SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.])
Tmin, Tmax 0.103, 0.146 0.31, 0.39
No. of measured, independent and observed [I > 2σ(I)] reflections 15054, 4062, 3964 24810, 3611, 3387
Rint 0.037 0.029
(sin θ/λ)max (Å−1) 0.649 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.045, 1.05 0.021, 0.053, 1.07
No. of reflections 4062 3611
No. of parameters 221 207
No. of restraints 1 0
H-atom treatment H-atom parameters constrained H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.25, −0.38 0.31, −0.26
Absolute structure Flack x determined using 1806 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]) –
Absolute structure parameter 0.010 (9) –
Computer programs: KappaCCD Server Software (Nonius, 1997[Nonius (1997). KappaCCD Server Software. Nonius BV, Delft, The Netherlands.]), DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

In (I)[link], μ3-CN cyanide groups C1≡N1 and C2≡N2 were found to be ordered, with the C atom bridging two Cu atoms, as in Corfield et al. (2016[Corfield, P. W. R., Cleary, E. & Michalski, J. F. (2016). Acta Cryst. E72, 892-896.]). In addition, C5≡N5 was found to have a clearly preferred orientation and was refined as an ordered group. C,N occupancy factors were refined for the two other cyanide groups, with preferential occupancies of 79 (3)% and 78 (3)% found for C3≡N3 and C4≡N4, respectively. Only the major C or N atoms are listed in the cif tables of bond lengths and bond angles. In (II)[link], all the CN groups are ordered; CN orientations were checked by refinements with inter­change of each CN group in turn, in each case resulting in significantly higher R factors.

In both compounds, C-bound H atoms were constrained to idealized positions with C—H distances of 0.97 Å for CH2 groups and 0.96 Å for CH3 groups, and Ueq values fixed at 1.2 times the Uiso of their bonded C atoms. The methyl torsion angles were refined. In (II)[link], the N- and O-bound hydrogen atoms were clearly visible in the difference-Fourier map and were refined independently. The N-bound hydrogen atoms in (I)[link] were clearly seen in a near-final difference map, and could be independently refined, but we chose to constrain them to idealized positions, with N—H distances of 0.90 Å for NH2 groups, 0.91 Å for NH groups, and Ueq values treated the same as for the C—H atoms.

For both (I)[link] and (II)[link], data had been previously collected with a CAD-4 system (Enraf–Nonius, 1994[Enraf-Nonius (1994). CAD-4. Enraf-Nonius, Delft, The Netherlands.]), on three crystals in the case of (I)[link], and two crystals for (II)[link]. For (I)[link], final R1 factors for the CAD-4 data were 0.045 for 2228 data with F2 > 2σ, while for (II)[link], R1 was 0.036 for 2245 data with F2 > 2σ. It was felt instructive to compare refined parameters obtained by the two methods. We defined Δ/σ for a given parameter as the absolute value of the difference between the parameters determined by the two instruments divided by the square root of the sum of the squares of the standard deviations for the two parameters. For (I)[link], the structural parameters agreed very well, for the mean and maximum Δ/σ for all parameters were 0.74 and 2.60. The maximum deviation for bond lengths was 2.1σ. For (II)[link], there were differences of 4–5σ between positional parameters for the water oxygen atom, O1, which was much better defined in the data set from the KappaCCD instrument. Apart from parameters for O1, the agreement was excellent, with average Δ/σ for positional parameters 0.79, and no Δ/σ greater than 3. There were differences in the Uij for the two Cu atoms because an extinction parameter was refined for the KappaCCD data set. For all other atoms, the mean Δ/σ for the thermal parameters was 0.83 with only one Δ/σ greater than 3.

Supporting information

CCDC references: 1525492; 1525491

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989017000111/pk2594sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017000111/pk2594Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017000111/pk2594IIsup3.hkl

checkCIF report


Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) Poly[bis(µ3-cyanido-κ3C:C:N)tris(µ2-cyanido-κ2C:N)bis(N-methylethane-1,2-diamine\- κ2N,N')tricopper(I)copper(II)] top
Crystal data top
[Cu4(CN)5(C3H10N2)2]F(000) = 1060
Mr = 532.52Dx = 1.985 Mg m−3
Dm = 2.01 (7) Mg m−3
Dm measured by flotation in 1,2-dibromopropane/1,2,3-trichloropropane mixtures. Three independent determinations were made.
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2c -2nCell parameters from 474 reflections
a = 19.509 (2) Åθ = 1.8–20.2°
b = 8.2306 (13) ŵ = 4.72 mm−1
c = 11.100 (2) ÅT = 303 K
V = 1782.3 (5) Å3Block cut from large polyhedral crystal, black
Z = 40.5 × 0.4 × 0.4 mm
Data collection top
Enraf–Nonius KappaCCD
diffractometer		4062 independent reflections
Radiation source: fine-focus sealed tube3964 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 2.1°
combination of ω and φ scansh = 0→25
Absorption correction: part of the refinement model (ΔF)
(SCALEPACK; Otwinowski & Minor, 1997)		k = 0→10
Tmin = 0.103, Tmax = 0.146l = −14→14
15054 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.045 w = 1/[σ2(Fo2) + (0.022P)2 + 0.040P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4062 reflectionsΔρmax = 0.25 e Å−3
221 parametersΔρmin = −0.38 e Å−3
1 restraintAbsolute structure: Flack x determined using 1806 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.010 (9)
Special details top

Experimental. Scalepack values for Tmin and Tmax are normalized to unity. Values given here were obtained by multiplying them by exp(-µd) where d= 0.45mm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.07836 (2)0.38153 (5)0.00021 (3)0.02552 (9)
Cu20.06847 (2)0.28058 (5)0.21765 (4)0.03143 (10)
Cu30.20761 (2)0.76738 (5)0.26057 (4)0.03009 (10)
Cu4−0.11518 (2)−0.01338 (4)0.15874 (4)0.02352 (9)
C10.00592 (15)0.2214 (4)0.0390 (3)0.0252 (6)
N1−0.03914 (15)0.1363 (3)0.0471 (3)0.0358 (7)
C20.12936 (15)0.4885 (4)0.1399 (3)0.0279 (7)
N20.16340 (14)0.5829 (3)0.1840 (2)0.0318 (6)
C30.12207 (16)0.0852 (4)0.2405 (3)0.0326 (9)0.79 (3)
N30.15237 (15)−0.0341 (4)0.2510 (3)0.0402 (9)0.79 (3)
N3A0.12207 (16)0.0852 (4)0.2405 (3)0.0326 (9)0.21 (3)
C3A0.15237 (15)−0.0341 (4)0.2510 (3)0.0402 (9)0.21 (3)
C4−0.00363 (15)0.6193 (4)−0.1714 (3)0.0270 (8)0.78 (3)
N40.03183 (14)0.5501 (4)−0.1084 (3)0.0298 (7)0.78 (3)
N4A−0.00363 (15)0.6193 (4)−0.1714 (3)0.0270 (8)0.22 (3)
C4A0.03183 (14)0.5501 (4)−0.1084 (3)0.0298 (7)0.22 (3)
C50.20639 (16)0.2799 (4)−0.1578 (3)0.0274 (7)
N50.15765 (14)0.3019 (4)−0.1041 (3)0.0311 (6)
N11−0.03685 (14)−0.1076 (3)0.2519 (3)0.0332 (6)
H11A−0.0058−0.03100.26670.040*
H11B−0.0518−0.14620.32210.040*
C12−0.00592 (18)−0.2392 (4)0.1810 (4)0.0410 (9)
H12A0.0220−0.30800.23230.049*
H12B0.0230−0.19460.11810.049*
C13−0.06375 (19)−0.3366 (5)0.1261 (3)0.0385 (8)
H13A−0.0455−0.42070.07400.046*
H13B−0.0906−0.38800.18900.046*
N14−0.10737 (15)−0.2222 (3)0.0553 (3)0.0310 (6)
H14−0.0807−0.1925−0.01610.037*
C15−0.1702 (2)−0.3019 (5)0.0107 (4)0.0465 (9)
H15A−0.1581−0.3981−0.03330.056*
H15B−0.1945−0.2286−0.04130.056*
H15C−0.1988−0.33070.07770.056*
N16−0.19542 (14)0.0806 (4)0.0694 (3)0.0329 (6)
H16A−0.18750.0790−0.00960.040*
H16B−0.23310.02300.08430.040*
C17−0.2044 (2)0.2508 (5)0.1118 (4)0.0470 (10)
H17A−0.24840.29330.08630.056*
H17B−0.16850.31990.07970.056*
C18−0.2003 (2)0.2437 (5)0.2477 (4)0.0479 (10)
H18A−0.20190.35280.28050.058*
H18B−0.23920.18350.27900.058*
N19−0.13606 (15)0.1637 (3)0.2845 (3)0.0326 (6)
H19−0.10000.24560.27550.039*
C20−0.1379 (2)0.1228 (5)0.4134 (4)0.0493 (10)
H20A−0.14950.21800.45910.059*
H20B−0.09380.08370.43810.059*
H20C−0.17170.04010.42700.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02310 (16)0.02762 (19)0.02583 (18)−0.00503 (14)0.00102 (15)−0.00028 (16)
Cu20.0336 (2)0.0315 (2)0.0292 (2)0.00564 (16)0.00206 (18)−0.00226 (18)
Cu30.0263 (2)0.0298 (2)0.0342 (2)−0.00366 (15)−0.00764 (16)−0.00447 (18)
Cu40.02156 (16)0.02424 (18)0.02476 (16)−0.00003 (14)−0.00319 (14)0.00006 (16)
C10.0245 (14)0.0257 (15)0.0254 (14)−0.0005 (12)0.0016 (12)−0.0003 (12)
N10.0315 (15)0.0403 (17)0.0357 (15)−0.0123 (13)−0.0017 (12)0.0058 (14)
C20.0212 (12)0.0253 (15)0.037 (2)0.0006 (11)−0.0041 (14)−0.0099 (14)
N20.0294 (14)0.0266 (13)0.0393 (17)0.0029 (12)−0.0061 (12)−0.0057 (12)
C30.0304 (16)0.0313 (19)0.0362 (18)−0.0003 (13)−0.0063 (14)−0.0003 (14)
N30.0344 (16)0.0287 (17)0.057 (2)0.0015 (13)−0.0138 (16)−0.0037 (15)
N3A0.0304 (16)0.0313 (19)0.0362 (18)−0.0003 (13)−0.0063 (14)−0.0003 (14)
C3A0.0344 (16)0.0287 (17)0.057 (2)0.0015 (13)−0.0138 (16)−0.0037 (15)
C40.0283 (15)0.0289 (16)0.0238 (15)−0.0012 (12)0.0002 (13)−0.0014 (13)
N40.0314 (15)0.0315 (15)0.0266 (14)−0.0005 (13)0.0004 (13)0.0030 (12)
N4A0.0283 (15)0.0289 (16)0.0238 (15)−0.0012 (12)0.0002 (13)−0.0014 (13)
C4A0.0314 (15)0.0315 (15)0.0266 (14)−0.0005 (13)0.0004 (13)0.0030 (12)
C50.0253 (15)0.0267 (16)0.0302 (16)−0.0017 (12)0.0048 (13)−0.0010 (13)
N50.0243 (13)0.0395 (16)0.0294 (14)0.0022 (12)0.0009 (12)−0.0018 (12)
N110.0285 (14)0.0406 (16)0.0304 (14)−0.0012 (11)−0.0032 (12)0.0102 (13)
C120.0286 (17)0.044 (2)0.050 (2)0.0134 (15)0.0098 (15)0.0161 (17)
C130.0449 (19)0.0286 (17)0.042 (2)0.0111 (15)0.0160 (16)0.0038 (16)
N140.0369 (15)0.0304 (14)0.0256 (13)−0.0031 (12)0.0052 (12)0.0006 (12)
C150.056 (2)0.044 (2)0.040 (2)−0.0105 (19)0.000 (2)−0.0112 (18)
N160.0282 (13)0.0346 (15)0.0361 (15)−0.0009 (12)−0.0053 (12)−0.0008 (13)
C170.048 (2)0.034 (2)0.059 (3)0.0104 (17)−0.010 (2)0.0016 (18)
C180.039 (2)0.042 (2)0.063 (3)0.0087 (16)−0.002 (2)−0.011 (2)
N190.0332 (14)0.0287 (14)0.0360 (16)−0.0042 (12)−0.0013 (12)−0.0056 (12)
C200.066 (3)0.048 (2)0.0340 (19)−0.005 (2)0.0050 (19)−0.0140 (17)
Geometric parameters (Å, º) top
Cu1—C11.980 (3)C12—C131.512 (6)
Cu1—C22.042 (3)C12—H12A0.9700
Cu1—N42.050 (3)C12—H12B0.9700
Cu1—N52.041 (3)C13—N141.493 (5)
Cu1—Cu22.5599 (7)C13—H13A0.9700
Cu2—C12.379 (3)C13—H13B0.9700
Cu2—C22.255 (3)N14—C151.475 (5)
Cu2—C31.935 (3)N14—H140.9800
Cu2—C4i1.948 (3)C15—H15A0.9600
Cu3—N21.942 (3)C15—H15B0.9600
Cu3—N3ii1.961 (3)C15—H15C0.9600
Cu3—C5iii1.910 (3)N16—C171.488 (5)
Cu4—N112.002 (3)N16—H16A0.8900
Cu4—N142.072 (3)N16—H16B0.8900
Cu4—N162.009 (3)C17—C181.512 (7)
Cu4—N192.059 (3)C17—H17A0.9700
Cu4—N12.292 (3)C17—H17B0.9700
C1—N11.127 (4)C18—N191.474 (5)
C2—N21.133 (4)C18—H18A0.9700
C3—N31.152 (4)C18—H18B0.9700
C4—N41.137 (4)N19—C201.470 (5)
C5—N51.136 (4)N19—H190.9800
N11—C121.469 (5)C20—H20A0.9600
N11—H11A0.8900C20—H20B0.9600
N11—H11B0.8900C20—H20C0.9600
C1—Cu1—C2118.01 (13)N11—C12—H12A110.2
C1—Cu1—N4105.22 (12)C13—C12—H12A110.2
C1—Cu1—N5116.79 (13)N11—C12—H12B110.2
C2—Cu1—N4111.75 (12)C13—C12—H12B110.2
C2—Cu1—N5101.54 (12)H12A—C12—H12B108.5
N4—Cu1—N5102.67 (12)C12—C13—N14107.6 (3)
C1—Cu1—Cu261.64 (10)C12—C13—H13A110.2
C2—Cu1—Cu257.36 (9)C12—C13—H13B110.2
N4—Cu1—Cu2137.79 (8)N14—C13—H13A110.2
N5—Cu1—Cu2119.22 (8)N14—C13—H13B110.2
C1—Cu2—C296.13 (11)H13A—C13—H13B108.5
C1—Cu2—C3102.49 (12)C13—N14—C15111.7 (3)
C1—Cu2—C4i106.29 (12)C13—N14—Cu4105.9 (2)
C2—Cu2—C3113.35 (12)C15—N14—Cu4119.6 (2)
C2—Cu2—C4i105.25 (12)C13—N14—H14106.3
C3—Cu2—C4i128.27 (13)C15—N14—H14106.3
C1—Cu2—Cu147.10 (7)Cu4—N14—H14106.3
C2—Cu2—Cu149.69 (8)N14—C15—H15A109.5
C3—Cu2—Cu1110.66 (10)N14—C15—H15B109.5
C4i—Cu2—Cu1120.51 (9)N14—C15—H15C109.5
N2—Cu3—C5iii129.79 (13)H15A—C15—H15B109.5
N2—Cu3—N3ii112.56 (12)H15A—C15—H15C109.5
N3ii—Cu3—C5iii117.64 (13)H15B—C15—H15C109.5
N11—Cu4—N1484.76 (12)C17—N16—Cu4107.3 (2)
N16—Cu4—N1984.72 (12)C17—N16—H16A110.2
N11—Cu4—N16178.39 (13)C17—N16—H16B110.2
N14—Cu4—N19167.74 (11)Cu4—N16—H16A110.2
N11—Cu4—N1994.30 (12)Cu4—N16—H16B110.2
N14—Cu4—N1695.92 (12)H16A—N16—H16B108.5
N1—Cu4—N1189.64 (11)N16—C17—C18105.8 (3)
N1—Cu4—N1495.67 (11)N16—C17—H17A110.6
N1—Cu4—N1691.74 (12)N16—C17—H17B110.6
N1—Cu4—N1996.55 (11)C18—C17—H17A110.6
N1—C1—Cu1170.9 (3)C18—C17—H17B110.6
N1—C1—Cu2117.4 (3)H17A—C17—H17B108.7
Cu1—C1—Cu271.26 (10)C17—C18—N19109.8 (3)
C1—N1—Cu4151.8 (3)C17—C18—H18A109.7
N2—C2—Cu1155.4 (3)C17—C18—H18B109.7
N2—C2—Cu2131.6 (3)N19—C18—H18A109.7
Cu1—C2—Cu272.94 (9)N19—C18—H18B109.7
C2—N2—Cu3170.2 (3)H18A—C18—H18B108.2
N3—C3—Cu2177.3 (3)C18—N19—C20110.6 (3)
C3—N3—Cu3iv176.5 (3)C18—N19—Cu4107.2 (2)
N4—C4—Cu2v174.9 (3)C20—N19—Cu4120.2 (2)
C4—N4—Cu1166.0 (3)Cu4—N19—H19106.0
N5—C5—Cu3vi172.9 (3)C18—N19—H19106.0
C5—N5—Cu1169.4 (3)C20—N19—H19106.0
C12—N11—Cu4108.8 (2)N19—C20—H20A109.5
Cu4—N11—H11A109.9N19—C20—H20B109.5
Cu4—N11—H11B109.9N19—C20—H20C109.5
C12—N11—H11A109.9H20A—C20—H20B109.5
C12—N11—H11B109.9H20A—C20—H20C109.5
H11A—N11—H11B108.3H20B—C20—H20C109.5
N11—C12—C13107.5 (3)
N14—C13—C12—N1156.0 (4)C20—N19—C18—C17−167.4 (3)
N19—C18—C17—N1654.6 (4)C15—N14—Cu4—N11141.85 (19)
C15—N14—C13—C12−172.8 (3)C20—N19—Cu4—N16133.9 (2)
Symmetry codes: (i) −x, −y+1, z+1/2; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, z+1/2; (iv) x, y−1, z; (v) −x, −y+1, z−1/2; (vi) −x+1/2, y−1/2, z−1/2.
(II) [(N-Methylethylenediamine-κ2N,N')copper(II)]-µ2-cyanido-κ2C:N-[bis(cyanido-κC)copper(I)] monohydrate top
Crystal data top
[Cu2(CN)3(C3H10N2)2]·H2OZ = 2
Mr = 371.42F(000) = 382
Triclinic, P1Dx = 1.566 Mg m−3
Dm = 1.570 (5) Mg m−3
Dm measured by flotation in 1,2-dibromopropane/1,2,3-trichloropropane mixtures. Four independent determinations were made.
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 7.5621 (2) ÅCell parameters from 3501 reflections
b = 8.8689 (2) Åθ = 1.8–27.5°
c = 12.8098 (3) ŵ = 2.70 mm−1
α = 94.6851 (14)°T = 300 K
β = 101.8607 (12)°Block cut from large elongated plate, blue
γ = 108.3780 (13)°0.5 × 0.4 × 0.3 mm
V = 787.91 (3) Å3
Data collection top
Enraf–Nonius KappaCCD
diffractometer		3611 independent reflections
Radiation source: fine-focus sealed tube3387 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.0°
combination of ω and φ scansh = 0→9
Absorption correction: part of the refinement model (ΔF)
(SCALEPACK; Otwinowski & Minor, 1997)		k = −11→10
Tmin = 0.31, Tmax = 0.39l = −16→16
24810 measured reflections
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.023P)2 + 0.270P]
where P = (Fo2 + 2Fc2)/3
3611 reflections(Δ/σ)max = 0.001
207 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Special details top

Experimental. Scalepack values for Tmin and Tmax are normalized to unity. Values given here were obtained by multiplying them by exp(-µd) where d= crystal_size_mid.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.44394 (3)0.21586 (2)0.789560 (16)0.04033 (7)
Cu20.98671 (2)0.744243 (19)0.753969 (13)0.03124 (7)
O10.1896 (5)−0.2985 (3)0.4215 (2)0.0992 (8)
C10.6318 (2)0.41700 (18)0.77647 (12)0.0379 (3)
N10.7425 (2)0.53316 (17)0.76709 (12)0.0461 (3)
C20.3303 (3)0.0522 (2)0.66225 (15)0.0488 (4)
N20.2639 (3)−0.0419 (2)0.58678 (15)0.0696 (5)
C30.3714 (3)0.1763 (2)0.92430 (15)0.0503 (4)
N30.3261 (3)0.1471 (2)1.00140 (15)0.0714 (5)
N40.9197 (2)0.91902 (18)0.83087 (11)0.0393 (3)
H4A0.841 (3)0.877 (3)0.8693 (18)0.056 (6)*
H4B1.009 (3)0.981 (3)0.8724 (18)0.057 (6)*
C50.8289 (3)0.9995 (2)0.75082 (15)0.0544 (4)
H5A0.92651.08690.73250.065*
H5B0.74431.04390.78040.065*
C60.7160 (3)0.8774 (2)0.65180 (14)0.0494 (4)
H6A0.60800.79760.66800.059*
H6B0.66680.92960.59470.059*
N70.8438 (2)0.79978 (16)0.61706 (10)0.0377 (3)
H70.927 (3)0.868 (2)0.5989 (14)0.036 (4)*
C80.7415 (4)0.6680 (3)0.52599 (15)0.0650 (6)
H8A0.65820.57940.55040.078*
H8B0.83300.63370.49760.078*
H8C0.66670.70490.47050.078*
N141.1101 (3)0.6146 (2)0.67452 (13)0.0494 (4)
H14A1.025 (3)0.528 (3)0.6453 (18)0.058 (7)*
H14B1.150 (4)0.660 (3)0.631 (2)0.070 (7)*
C151.2645 (3)0.5852 (3)0.75204 (19)0.0673 (6)
H15A1.38540.67130.75940.081*
H15B1.27850.48470.72620.081*
C161.2143 (3)0.5773 (2)0.85903 (16)0.0529 (4)
H16A1.10290.48280.85430.064*
H16B1.32080.57110.91340.064*
N171.1722 (2)0.72477 (17)0.88834 (11)0.0426 (3)
H171.266 (3)0.798 (3)0.8945 (16)0.047 (5)*
C181.1031 (3)0.7205 (2)0.98757 (14)0.0569 (5)
H18A0.97430.64560.97250.068*
H18B1.10480.82571.01350.068*
H18C1.18520.68731.04160.068*
H10.214 (4)−0.230 (3)0.458 (2)0.069 (8)*
H20.253 (5)−0.289 (4)0.392 (3)0.086 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03480 (11)0.03580 (11)0.04541 (12)0.00351 (8)0.01158 (8)0.00885 (8)
Cu20.03185 (10)0.02916 (10)0.03047 (10)0.00749 (7)0.00698 (7)0.00575 (7)
O10.136 (2)0.0550 (11)0.1022 (17)0.0208 (12)0.0481 (16)−0.0130 (11)
C10.0331 (7)0.0377 (8)0.0382 (8)0.0066 (6)0.0062 (6)0.0089 (6)
N10.0375 (7)0.0418 (7)0.0521 (8)0.0031 (6)0.0099 (6)0.0152 (6)
C20.0481 (9)0.0403 (8)0.0518 (10)0.0015 (7)0.0205 (8)0.0076 (7)
N20.0754 (12)0.0553 (10)0.0621 (11)−0.0037 (9)0.0292 (9)−0.0063 (8)
C30.0435 (9)0.0453 (9)0.0498 (10)−0.0028 (7)0.0145 (7)0.0035 (7)
N30.0725 (12)0.0741 (12)0.0616 (11)0.0064 (9)0.0326 (9)0.0116 (9)
N40.0424 (7)0.0391 (7)0.0358 (7)0.0129 (6)0.0104 (6)0.0043 (6)
C50.0739 (12)0.0538 (10)0.0511 (10)0.0395 (10)0.0190 (9)0.0134 (8)
C60.0477 (9)0.0651 (11)0.0446 (9)0.0282 (8)0.0129 (7)0.0201 (8)
N70.0416 (7)0.0374 (7)0.0330 (6)0.0101 (6)0.0105 (5)0.0103 (5)
C80.0863 (15)0.0552 (11)0.0399 (10)0.0241 (10)−0.0112 (9)0.0005 (8)
N140.0605 (10)0.0555 (10)0.0452 (8)0.0287 (8)0.0241 (8)0.0142 (7)
C150.0586 (12)0.0890 (16)0.0741 (14)0.0441 (12)0.0261 (10)0.0202 (12)
C160.0479 (10)0.0563 (10)0.0569 (11)0.0258 (8)0.0038 (8)0.0130 (8)
N170.0384 (7)0.0382 (7)0.0421 (7)0.0073 (6)−0.0003 (6)0.0046 (6)
C180.0737 (13)0.0592 (11)0.0359 (9)0.0262 (10)0.0025 (8)0.0113 (8)
Geometric parameters (Å, º) top
Cu1—C11.9434 (15)C6—H6B0.9700
Cu1—C21.9380 (18)N7—C81.470 (2)
Cu1—C31.9414 (18)N7—H70.810 (19)
Cu2—N12.2232 (14)C8—H8A0.9600
Cu2—N42.0200 (14)C8—H8B0.9600
Cu2—N72.0453 (13)C8—H8C0.9600
Cu2—N142.0262 (15)N14—C151.475 (3)
Cu2—N172.0417 (14)N14—H14A0.83 (2)
O1—H10.68 (3)N14—H14B0.77 (3)
O1—H20.66 (3)C15—C161.497 (3)
C1—N11.138 (2)C15—H15A0.9700
C2—N21.135 (2)C15—H15B0.9700
C3—N31.134 (2)C16—N171.478 (2)
N4—C51.474 (2)C16—H16A0.9700
N4—H4A0.86 (2)C16—H16B0.9700
N4—H4B0.78 (2)N17—C181.469 (2)
C5—C61.503 (3)N17—H170.78 (2)
C5—H5A0.9700C18—H18A0.9600
C5—H5B0.9700C18—H18B0.9600
C6—N71.467 (2)C18—H18C0.9600
C6—H6A0.9700
C1—Cu1—C2117.49 (7)C6—N7—C8112.25 (16)
C1—Cu1—C3122.15 (7)C6—N7—Cu2105.83 (10)
C2—Cu1—C3120.36 (7)C8—N7—Cu2117.11 (11)
N1—Cu2—N498.67 (6)C6—N7—H7107.8 (13)
N1—Cu2—N1495.33 (7)C8—N7—H7109.2 (13)
N1—Cu2—N1794.80 (6)Cu2—N7—H7104.0 (13)
N1—Cu2—N796.00 (6)N7—C8—H8A109.5
N4—Cu2—N784.33 (6)N7—C8—H8B109.5
N14—Cu2—N1784.09 (6)H8A—C8—H8B109.5
N4—Cu2—N14165.99 (7)N7—C8—H8C109.5
N7—Cu2—N17169.19 (6)H8A—C8—H8C109.5
N4—Cu2—N1794.23 (6)H8B—C8—H8C109.5
N7—Cu2—N1494.71 (6)C15—N14—Cu2109.64 (13)
H1—O1—H2109 (4)C15—N14—H14A110.0 (16)
N1—C1—Cu1178.61 (16)Cu2—N14—H14A107.1 (16)
C1—N1—Cu2172.56 (14)C15—N14—H14B110.8 (19)
N2—C2—Cu1178.96 (18)Cu2—N14—H14B109.6 (19)
C2—N2—H1163.7 (8)H14A—N14—H14B110 (2)
C2—N2—H7i99.5 (4)N14—C15—C16108.87 (15)
H1—N2—H7i93.6 (8)N14—C15—H15A109.9
N3—C3—Cu1177.36 (18)C16—C15—H15A109.9
C3—N3—H4Aii160.8 (6)N14—C15—H15B109.9
C3—N3—H4Bi83.4 (5)C16—C15—H15B109.9
H4Aii—N3—H4Bi85.9 (7)H15A—C15—H15B108.3
C5—N4—Cu2109.61 (10)N17—C16—C15107.60 (16)
C5—N4—H4A109.2 (15)N17—C16—H16A110.2
Cu2—N4—H4A109.7 (14)C15—C16—H16A110.2
C5—N4—H4B111.2 (17)N17—C16—H16B110.2
Cu2—N4—H4B112.3 (17)C15—C16—H16B110.2
H4A—N4—H4B105 (2)H16A—C16—H16B108.5
N4—C5—C6108.28 (14)C18—N17—C16111.46 (15)
N4—C5—H5A110.0C18—N17—Cu2115.52 (12)
C6—C5—H5A110.0C16—N17—Cu2105.30 (10)
N4—C5—H5B110.0C18—N17—H17111.6 (15)
C6—C5—H5B110.0C16—N17—H17107.8 (15)
H5A—C5—H5B108.4Cu2—N17—H17104.6 (15)
N7—C6—C5108.34 (14)N17—C18—H18A109.5
N7—C6—H6A110.0N17—C18—H18B109.5
C5—C6—H6A110.0H18A—C18—H18B109.5
N7—C6—H6B110.0N17—C18—H18C109.5
C5—C6—H6B110.0H18A—C18—H18C109.5
H6A—C6—H6B108.4H18B—C18—H18C109.5
N4—C5—C6—N7−53.1 (2)C18—N17—C16—C15174.49 (16)
N14—C15—C16—N17−53.0 (2)C8—N7—Cu2—N4−148.13 (15)
C8—N7—C6—C5174.98 (15)C18—N17—Cu2—N14−148.74 (14)
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+1, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.68 (3)2.13 (3)2.810 (3)171 (3)
N14—H14A···O1iii0.83 (2)2.14 (2)2.965 (3)177 (2)
N4—H4A···N3ii0.86 (2)2.26 (2)3.094 (2)161.1 (19)
N7—H7···N2iv0.810 (19)2.460 (19)3.162 (2)145.7 (16)
N4—H4B···N3iv0.78 (2)2.53 (2)3.302 (3)170 (2)
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y, −z+1; (iv) x+1, y+1, z.
 

Acknowledgements

We are grateful to the Office of the Dean at Fordham University for its generous financial support. We thank Fordham University students Emma Cleary and Phuong Luu for assistance with this work, and colleagues Paul Smith and Christopher Koenigsmann for assistance in setting up the KappaCCD system.

References

First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
 First citationCai, J.-B., Chen, T.-T., Xie, Z.-Y. & Deng, H. (2011). Acta Cryst. E67, m1136–m1137.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationCorfield, P. W. R., Cleary, E. & Michalski, J. F. (2016). Acta Cryst. E72, 892–896.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationCorfield, P. W. R. & Michalski, J. F. (2014). Acta Cryst. E70, m76–m77.  CSD CrossRef IUCr Journals Google Scholar
 First citationEnraf–Nonius (1994). CAD-4. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
 First citationEtaiw, S. H., Abdou, A. N. & Badr El-din, A. S. (2015). J. Inorg. Organomet. Polym. 25, 1394–1406.  Web of Science CSD CrossRef CAS Google Scholar
 First citationEtaiw, S. E. H., Badr El-din, A. S. & Abdou, A. N. (2016). Transition Met. Chem. 41, 413–425.  Web of Science CSD CrossRef CAS Google Scholar
 First citationGroom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationNonius (1997). KappaCCD Server Software. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWilliams, R. J., Larson, A. C. & Cromer, D. T. (1972). Acta Cryst. B28, 858–864.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 73| Part 2| February 2017| Pages 141-146
https://doi.org/10.1107/S2056989017000111
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS